Dyes of the diaminotriarylmethane series



United States Patent 01 hce US. Cl. 260393 23 Claims ABSTRACT OF THE DISCLOSURE This invention relates to basic dyes of the diaminotriarylmethane series of Formula I, their production and use.

Especially it relates to a process for the dyeing or printing of fibres, or textile materials made thereof, which consist of or which contain acrylonitrile polymers or copolymers. The process is characterised by the use of basic dyes of the diaminotriarylmethane series having the formula I R1 (I) where one of the symbols R and R stands for hydrogen and the other for a cyano, alkylsulphonyl, arylsulphonyl, alkylcarbonyl or arylcarbonyl radical or for a sulphonic acid amide or carboxylic acid amide radical which may be substituted, two of the radicals R stand for cyanalkyl or hydroxyalkyl, the remainding two radicals R for alkyl radicals which may be substituted, and X for an anion equivalent to the dye cation, and in which the rings B and/or D may be further substituted. Examples of good dyes of Formula I are those in which the aromatic rings B and D are substituted.

Dyeings of good quality are obtained when, for example, dyes of formula z z R I I Z 1 Z 1 NCH4C2\ I $/C2H4CN Alkyl Alkyl R1 (III) where each Z represents an alkyl or alkoxy radical having 1 to 4 carbon atoms and alkyl, a lower alkyl radical.

3,535,347 Patented Oct. 20, 1970 Dyes of Formula III in which each Z stands for a methyl, ethyl, methoxy or ethoxy radical are particularly Well suitable for use in the process.

Dyeings of the same good quality are obtained with the dyes of formula Ra-Alkylene l I Alkylene-Ra N o=-i x Rz-Alkylene I Alkylene-Ra where each R stands for the hydroxyl or cyano group and each Z for a hydrogen or halogen atom or for an alkyl or alkoxy radical, which latter radical may be substituted.

Particularly good dyeings are obtained when dyes of are used, for example dyes of this formula in which each Z represents an alkyl or alkoxy radical having 1 to 4 carbon atoms, more particularly a methyl, ethyl, methoxy or ethoXy radical.

Particularly good dyeings are given by dyes of Formula V in which Z denotes a methyl radical and R an optionally substituted sulphonic acid amide radical.

Excellent dyeings are obtained with dyes of Formula I in which R represents an optionally substituted sulphonic acid amide radical, and also with dyes of formula Alkyl l h (VI) in particular dyes of Formula VI in which alkyl represents an ethyl radical and R an optionally substituted sulphonic acid amide group.

The dyes of Formula I can be produced by condensing 1 mole of a compound of formula R2 (VII) with 2 moles of a compound of formula R (VIII) to form the leuco base of formula R\ III R and oxidizing this in acid solution by one of the known methods.

An alternative method of production for the dyes of Formula I is to react a compound of formula R (H) /R B R R (x) with a compound of formula It: (XI) to form the corresponding carbinol base and to convert this into a dye of Formula I by acid treatment.

Another route leading to the dyes of Formula I is to condense a compound of formula 11 (XII) with a compound of Formula XI to obtain the leuco base of Formula IX and to oxidise the base to the final dye.

Certain dyes of Formula I can be produced by exchanging the hydrogen in the 4-position of the ring E of a leuco base of formula for a cyano, alkylsulphonyl, arylsulphonyl, alkylcarbonyl or arylcarbonyl radical or for an optionally substituted sulphonic acid amide or carboxylic acid amide radical, and to oxidize the reaction product by one of the known methods.

The dyes of Formula I can be used either singly or in mixture with each other.

The alkyl radicals contain, e.g., l to 8 or preferably 1 to 4 carbon atoms.

The rings B and/or D may be substituted, for example by halogen, such as chlorine, bromine or fluorine, or by an optionally substituted alkyl or alkoxy radical having 1 to 10 or preferably 1 to 4 carbon atoms, e.g. CF It is of special advantage for two of the radicals R to stand for hydroxyethyl or cyanethyl radicals, while the other two radicals R represent, preferably, cyanethyl radicals or lower, unsubstituted or substituted alkyl radicals having 1 to 4 carbon atoms.

The anion X may be an organic or inorganic ion, e.g. a halogen ion, such as that of chlorine, bromine or iodine, or the ion of methylsulphate, sulphate, disulphate, perchlorate, phosphate, phosphotungstate, phosphotungstic molybdate, benzenesulphonate, 4-chlorobenzenesulphonate, oxalate, maleinate, formate, acetate, propionate, methanesulphonate, chloroacetate or benzoate, or a complex anion such as that of zinc chloride double salts.

Alkylene stands preferably for a radical of formula -(CH where n denotes a whole number from 1 to 6 preferably 2; this alkylene radical may be branched if desired.

Examples of alkyl sulphonyl radicals are those of formula R 40 where R; may stand for a substituted or unsubstituted alkyl radical having, for example, 1 to 6 carbon atoms. Arylsulphonyl radicals are those of the formula R -SO where R may stand for a substituted or unsubstituted phenyl or naphthyl radical.

Alkylcarbonyl radicals are of the formula -CO-R where R may stand for a substituted or unsubstituted alkyl radical having, for example, 1 to 6 carbon atoms.

Arylcarbonyl radicals are of the formula -COR7 where R may represent a phenyl or naphthyl radical which may be substituted. The sulphonic acid amide group stands for a radical of formula where each of the radicals R and R represents a hydrogen atom or an optionally substituted hydrocarbon radical, e.g. an alkyl, phenyl, naphthyl or cyclohexyl radical. The sulphonic acid amide group may be introduced by a subsequent reaction, for example when R or R stands for -SO rCl, by aminating the last-named group. The carboxylic acid amine group stands for a radical of formula The term acrylonitrile polymers is used with special reference to polymers consisting to more than of acrylonitrile. Acrylonitrile copolymers are composed, in general, of 8095% acrylonitrile and 20-5 vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, etc.

The dyes defined in the foregoing are applied to these materials preferably from an aqueous medium of neutral or acid reaction, and at boiling temperature or at temperatures above C. when closed dyeing equipment is used. The dyes of Formula I can be applied from aqueous solution or dispersion, if necessary in the presence of a dissolving intermediary, e.g. a polyglycol ether of a higher fatty alcohol. It is advisable to use approximately 0.2-1 gram of a polyglycolether to 1 gram of dye. The commercially available retarders can be used without causing interference, though they are not necessary since very level dyeings of good all-round fastness can be produced without their assistance.

US. Pat. 3,021,344 teaches the use of a dye of formula for the dyeing of polyacrylonitrile fibres that have been modified by the introduction of acid groups. This dye has poor light fastness on this type of polyacrylonitrile fibre.

It was surprising, since it was not inferable from the present state of the art, that dyes of Formula I would give dyeings on these modified polyacrylonitrile fibres showing better fastness to light than that of the known dye. In addition, these dyeings are very fast to wet tests, the fastness to washing, water, sea water, perspiration and milling being particularly good. The dyes preserve wool.

In the following examples the parts and percentages are by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 One part of the dye of formula 02H; CzHs NO= 01 Ho (Ia H4 I \C2H4ON SI OzNHz is pasted with 1 part of 40% acetic acid. 400 parts of dis- Equally good dyeings are obtained when the dye is initilled water at 60 are run on to the paste with constant tially pasted with 2/normal sulphuric acid, preferably stirring and the solution is boiled for a While to complete with 0.2 part, or with formic acid, for example 1 part of dissolving. It is then diluted with 7600 parts of distilled 80% formic acid. water, after which 2 parts of glacial acetic acid are added. The dyes enumerated in the following table can be dyed 100 parts of polyacrylonitrile material are entered into by the method described above. this dyebath at 60 after a previous treatment of 10-15 These dyes conform to the formula minutes at 60 in a bath of 8000 parts of water and v v 2 parts of glacial acetic acid. The dyebath is raised to n I m 100 in 30 minutes and held at this temperature for 1 10 fQ Anion 6 hour. On removal, the material is rinsed and dried. A I level, brilliant green dyeing is obtained which has good fastness to light and wet treatments Dyeings of comparable quality are obtained when the R2 dye used in this example or any of the dyes listed in 15 I the following table are applied in the presence of 0.2-1 R1 part of a polyglycol ether of a higher fatty alcohol in Where R1, R2, R10, R11, V and 9 h h meanings accordance with the procedure of Example 1. assigned t th i th t b1 Shade of dyeing on polyaerylo- Ex.No. R1 R2 R10 R V Anion X19 nitrile fibre 2 s 02N\ H CzH CzHlCN H 019 Green.

3 sozNHr H CH3(CH2)3- CZH4CN H H3049 D0.

4 S 02N\ H CH3 C2H4CN H 01 D0.

5 SOzNHCgEhOH H CH3 CzH ON H H8049 lDo.

C2H4OH 6 s OzN H CH3 C2H4CN H 019 Do.

C H OH 7 SOZCHS H CH3 CZH4CN H H3049 Do. 3-- SOzNHz H 02114011 CZH4OH H Iiooo D0.

SOzN(CH CH3 C2H4CN H 019 Blue-green. oN H CH3 C2H4CN H 016 Green.

SOgNH CZH5 CzHeCN H H3049 Blue-green. CONHz H C2135 CzH CN H oHaooo Green. COCH3 H CzH5 C2H4CN H CHaCOO Do.

CONHZ C2H5 C2H4CN H H8049 Blue-green. ZNH H C: 5 C2H4CN CH3 C19 Yellowish green. SO2N(CH3)5 H CzH5 OzH CN OCH3 C 9 Green. H C H OH C2H4OH H CH3COO9 Do SOzNHz H CZH4OH C2H4CN H CHaCOO Do SOzNHg C2H4OH 02H40N H 011 000 Do H CN CH C H CN H CHaCOO Do H SOz-N(CH3)2 C2H5 C2H4CN H 01130009 Do H s 20H, ogHfi OZHrCN H CHaCOO Do COCH3 CzH CQH4CN H omooo D0 SOz--NH2 H C2115 CzH CN one oHaoooe Do. SOz-NHz H CgHqCN CzH4CN H Hoooe Bluish green: SO2NH2 H C2H4OH CZH4OH 0H3 H0009 Green.

SOzNHz CzHeCN CgHeCN czHroN (3113000 Yellowish green. H SOzNHz CzH CN C2H4CN H 016 Green. H SOzNHz C H4OH C2H40H H H3049 o. H SO2-N(CH3)Z GzHaCN CZH4CN CH3 H0009 D0, SOg-NH2 H C2H4CN 0QH40N OCH CHaCOO Do. SO -NH-CgH H C2H4ON ozHroN CH3 Hoooe D0. 33 SO2-N(CH H C2H4CN CzH-iCN CH3 H000 Do.

34 SOz-N-CHs H C2H4CN C2H4CN CH3 01130009 D0.

7 EXAMPLE 46 A mixture of 42.6 parts of 1-N,N-di-(2'-cyanoethyl)- amino-3-methylbenzene, 10.6 parts of benzaldehyde, 100 parts of isopropyl alcohol, 20 parts of 37% sulphuric acid and 5 parts of urea is stirred for 3 hours at 70 under a jet of nitrogen. The reaction product settles out in crystalline form and on cooling it is filtered off; the leuco base thus obtained melts at 168. Over 2 hours, 51.4 parts of this leuco base are entered with ice-cooling into a mixture of 160 parts of chlorosulphonic acid and 24 parts of thionyl chloride. The mixture is stirred for 4-5 hours at -5, after which it is discharged into a mixture of 2200 parts of ice and 575 parts of concentrated ammonia, and the product filtered off, washed with water and dried. 59.2 parts of the leuco base thus obtained are dissolved in 400 parts of 37% sulphuric acid, and to this solution a solution of 10 parts of sodium bichromate in 30 parts of water is added at 10-15 with stirring. A dye is formed which has the formula It dyes polyacrylonitrile fibres in brilliant green shades which have excellent ligh fastness and very good wet fastness properties.

EXAMPLE 47 A mixture of 42.6 parts of 1-N,N-di-(2'-cyanoethyl)- amino-3-methylbenzene, 20 parts of benzaldehyde-4-sulphonic acid amide, 100 parts of isopropyl alcohol, 20 parts of 37% sulphuric acid and 5 parts of urea is stirred for 3 hours at 70 under an injected nitrogen atmosphere. The reaction product crystallises out and, after cooling, it is filtered off. 51.4 parts of the resulting leuco base are dissolved in 400 parts of 37% sulphuric acid, to which is added dropwise at 15 a solution of 10 parts of sodium bichromate in 30 parts of water. The dye formed, which has the formula is filtered off, washed with water until free of acid, and dried with vacuum. It dyes polyacrylonitrile fibres in brilliant green shades having good fastness to light and wet treatments.

EXAMPLE 48 parts of the dye used in Example 1 and 80 parts of dextr in are intimately mixed in a ball mill for 48 hours. A prlnting paste is then prepared with the following additions:

75 parts of the ground dyeing preparation,

10 parts of concentrated acetic acid,

450 parts of sodium alginate thickening,

parts of a cationic softener, e.g. the concentration product of equimolar amounts of stearic acid and triethanolamine,

25 parts of Glaubers salt and 415 parts of water 1000 parts Having thus disclosed the invention what I claim is: 1. Basic dye of the diaminotriarylmethane series of the formula wherein one of R and R is hydrogen and the other is a member selected from the group consisting of cyano, alkylsulphonyl, arylsulphonyl, alkylcarbonyl, arylcarbonyl, sulphonic acid amide and carboxylic acid amide; each alkyl of alkylsulphonyl or alkylcarbonyl is alkyl having from 1 to 6 carbon atoms; each aryl of arylsulphonyl and arylcarbonyl is either phenyl or naphthyl; I sulphonic acid amide is a radical of the formula carboxylic acid amide is a radical of the formula CO--N(R )R each of R and R is, independently, a member selected from the group consisting of a hydrogen atom, alkyl and hydroxyalkyl having from 1 to 8 carbon atoms, phenyl, naphthyl and cyclohexyl; at least two of the radicals R are cyanalkyl or hydroxyalkyl, the alkyl of which contains from 1 to 6 carbon atoms; any remaining radicals R are alkyl radicals, each containing from 1 to 8 carbon atoms; X is an anion equivalent to the dye cation; and each of rings B and D is either further unsubstituted or further substituted, any 'substituent thereon being a member selected from the group consisting of halo, lower alkyl, lower alkoxy, cyano(lower)alkyl and fluoro (lower) alkyl. 2. Basic dye according to claim 1 wherein each of rings B and D is further substituted.

3. Basic dye according to claim 2 wherein each of rings B and D is substituted in a position ortho to the methane carbon.

4. Basic dye according to claim 1 of the formula Z 1 Z 1 NC-H4C2\ eB/CzHaCN Xe Alkyl Alkyl where each Z represents an alkyl or alkoxy radical having 1 to 4 carbon atoms and alkyl a lower alkyl radical. 5. Basic dye according to claim 4 of the Formula III, in which each Z stands for a methyl, ethyl, methoxy or ethoxy radical.

6. Basic dye according to claim 1 of the formula each R is a member selected from the group consisting of hydroxy and cyano; and

each Z is a member selected from the group consisting of hydrogen, halo, lower alkyl, lower alkoxy, cyano (lower)alkyl and flnoro(lower)alkyl.

7. The basic dye according to claim 1 of the formula 8. The basic dye according to claim 1 of the formula I S Oz-CHS 9. The basic dye according to claim 1 or the formula CH CH3 HaC2\ Q/C2H5 /N ('3: N\ 019 NCH4C2 C2H4CN S 02-NH2 10. The basic dye according to claim 1 of the formula CH3 CH3 NC-H4C2 I C2H4-CN B/ I no 0 0 NO-H4Cz CzH4-CN l O OGH;

11. The basic dye according to claim 1 of the formula CH3 CH2 NC-H4Cz I I C2H4-CN 65/ e /N (|J= :N\ 11804 NC--H2C2 C2H4-CN S Or-NHZ 12. Basic dye according to claim 1 of the formula Z1 Z1 NCH4C2\ /CH4CN :3 X9 NCH4C2 CzH4CH in which each Z represents alkyl or alkoxy having 1 to 4 carbon atoms.

13. Basic dye according to claim 12 wherein each Z is a member selected from the group consisting of methyl, ethyl, methoxy and ethoxy.

14. Basic dye according to claim 12 wherein each Z is methyl and R is a sulphonic acid amide.

15. Basic dye according to claim 1 wherein R is a sulphonic acid amide.

16. Basic dye according to claim 1 of the formula l R R wherein each R contains two carbon atoms and R is a sulphonic acid amide.

V w I 69/Rio wherein one of R and R stands for hydrogen and the other for cyano, the sulphonic acid amide group, sulfonic acid mono(lower) alkylamide, sulfonic acid di(lower) alkylamide, sulfonic acid mono[hydroxy(lower) alkyl]amide, sulfonic acid di[hydroxy(lower) alkyl] amide, sulfonic acid monophenylamide, sulfonic acid N-(lower)alkyl-N-phenylamide, lower alkylsulfonyl, (lower)alkylphenylsulfonyl, or aminocarbonyl;

V stands for hydrogen, lower alkyl, lower alkoxy,

trifluoromethyl or cyanethyl;

R stands for lower alkyl, cyanethyl or hydroxyethyl;

R stands for cyanethyl or hydroxyethyl; and

X for an anion equivalent to the dye cation.

18. Basic dye according to claim 17 in which each V is lower alkyl or lower alkoxy.

19. Basic dye according to claim 17 of the formula wherein each Z is alkyl or alkoxy having 1 to 4 carbon atoms;

and

R is lower alkyl.

20. Basic dye according to claim 17 of the formula each R is hydroxy or cyano; and each Z is a hydrogen atom, lower alkyl or lower alkoxy.

21. Basic dye according to claim 17 of the formula CH3 CH3 wherein R is the sulfonic acid amide group, sulfonic acid mono- (lower) alkylamide, sulfonic acid di(lower alkyl)amide, sulfonic acid mono[hydroxy(lower) alkyl] amide, sulfonic acid di[hydroxy(lower)alkyl]amide, sulfonic acid monophenylamide or sulfonic acid N-(lower)alkyl-N-phenyla'mide.

22. Basic dye according to claim 17 of the formula wherein R is the sulfonic acid amide group, sulfonic acid mono- (lower) alkylamide, sulfonic acid di(lower alkyl)amide, sulfonic acid mono[hydroxy(lower)alkyl]amide, sulfonic acid di[hydroxy(lower)alkyl]amide, sulfonic acid monophenylamide or sulfonic acid N-(lower)alkyl-N-pheny1- amide.

23. Basic dye according to claim 17 of the formula H H NC-Hicz I C 2114- C N wherein R is the sulfonic acid amide group, sulfonic acid mono- (lower)alkylamide, sulfonic acid di(lower alkyl)amide, sulfonic acid mono [hydroxy(lower) alkyl]amide, sulfonic acid di[hydroxy(lower)alkyl]amide, sulfonic acid monophenylamide, sulfonic acid N-(lower)alkyl-N-pheny1- amide.

References Cited UNITED STATES PATENTS 2,085,736 7/1937 Calcott et al 260394 LORRAINE A. WEINBERGER, Primary Examiner L. A. THAXTON, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,535,347 Dated October 20, 1970 Inventorfli) PETER BITTERLI It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 38, "remainding" should read -remaining; line 57, "optionaly" should read optionally-. Column 3, line 65, "6' should read -6,--. Column 4, line 60, "preserve" should read -reserve. Column 5, line 6, "60" should read -60 Columns 5 and 6, heading of sixth column of table, "Anion X should read Anion li Column 8, line 25, "SO-CH should read --S0 CH line 32, "C H CN should read --C H CN--. Column 9, line 6, "-S0 N(R )R should read S0 N(R )R line 9, "C0-N(R )R should read C0-N(R )R Column 10, line 25, "N=" should read N- line 34, "CH should read CH line 37 "NC-H C should read NC-H C Column 12,

2 2 4 2 line 40,

Signed and sealed this 27th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSGHALK Attesting Officer Commissioner of Patents FORM P04 uo'sg) USCOMM-DC 60376-P59 9 U 5' GOVERNMENY PRINTING DFFICE I96! 0-366-331 

